The preparation of enatiomerically enriched homoallylic alcohols through asymmetric addition of chiral allylic transfer reagents and allylating reagents with chiral catalysts to the carbonyl functionalities represents an important chemical transformation. Excellent progress has been made over past decade in the development and application of catalytic asymmetric allylic transfer reactions. In this account, our efforts for the various intermolecular allylic transfer reactions such as allylation, propargylation, allenylation, and dienylation utilizing accelerating strategy and sequential allylic transfer reactions to achieve multiple stereoselection mainly using transition metal catalysts are described.

We developed a microfluidic immunoassay platform for the detection of various analytes such as bacterial pathogen by packing antibody-immobilized glass beads in spatially-isolated microchambers on a microfluidic device. Primary amines of antibody were covalently conjugated to carboxyl-terminated glass beads previously treated with aminosilane followed by glutaraldehyde. Through this covalent binding, up to 905 g immunoglobulin G (IgG) per gram of glass beads was immobilized. For application, glass beads attaching antibody specific to Escherichia coli O157:H7, a foodborne pathogen, were packed into a microfluidic device and used for the detection of the serotype. This prototype immunoassay device can be used for the simultaneous detection of multiple analytes by sequentially packing different-sized glass beads attaching different antibody in discrete microchambers on a single microfluidic device.

The solid-phase synthesis of new series of 1,6,8-trisubstituted tetrahydro-2H-pyrazino[1,2-a]pyrimidine-4,7-diones as bicyclic -turn mimetics is described. Their NF-kB inhibition activities were tested and the effect of substituents on bicyclic ring was investigated. Among the prepared compounds, the fluorobenzyl and methoxybenzyl group substituted compounds 26 and 27 at C-1 and C-8 position showed more inhibitory activities than the others. Tested at a concentration of 10 uM, these two compounds showed a 60% inhibition against the target NF kB 549. ꤠ 돀遠�⨀ 堘�⨀ 袢�⨀ 脠 돐 ꢢ�⨀ ࢷ�⨀ 낢�⨀ 夠 댐 쀅�⨀ 퀅?⨀ �⨀ ㄠ 덐 £�⨀ †

Goethite, hematite, magnetite and synthesized iron oxide are used as catalysts for Fenton-type oxidation of phenol. The synthesized iron oxides were characterized by X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR). The catalytic activity of these materials is classified according to the observed rate of phenol oxidation. The effectiveness of the catalysts followed the sequence: ferrous ion > synthesized iron oxide >> magnetite hematite > goethite. According to these results, the most effective iron oxide catalyst had the structure similar to natural hematite. The surface oxidation state of the catalyst was between magnetite and hematite (+2.5 ~ +3.0). Phenol degraded completely in 40 min at neutral pH (pH = 7). Soluble ferric and ferrous ions were not detected in the filtrate from Fenton reaction solution by AAS. The formation of hydroxyl radicals was confirmed by EPR.

Intramolecular energy flow and C- and C- bond dissociations in vibrationally excited toluene in the collision with HF have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited toluene upon collision is not large and it increases slowly with increasing total vibrational energy content between 20,000 and 45,000 . Above the energy content of 45,000 , however, energy loss decreases. Furthermore, in the highly excited toluene, toluene gains energy from incident HF. The temperature dependence of energy loss is negligible between 200 and 400 K. Energy transfer to or from the excited methyl C-H bond occurs in strong collisions with HF transferring relatively large amount of its translational energy (>> ) in a single step, whereas energy transfer to the ring C-H bond occurs in a series of small steps. When the total energy content of toluene is sufficiently high, either C-H bond can dissociate. The C- dissociation probability is higher than the C- dissociation probability. The dissociation of the ring C-H bond is not the result of the intermolecular energy flow from the direct collision between the ring C-H and HF but the intramolecular flow of energy from the methyl group to the ring C-H stretch. The C-HF interaction is not important in transferring energy and in turn bond dissociation.

The rhodium(II)-catalyzed reactions of diazo compound derived from Meldrum's acid with a variety of styrenes have been examined. These reactions provide a rapid route to the preparation of cyclopropanes with a variety of substituents on the benzene ring. The mechanistic pathway for the formation of these products has been also described in terms of a stepwise mechanism.

In this study, we have performed ab initio computer simulations to investigate the conformational and complexation characteristics of the trimethyl ether of p-tert-butylmonodeoxycalix[4]arene (6) with a potassium ion. The structures of different conformers of 6 and their potassium complexes were optimized by using ab initio RHF/6-31G and B3LYP/6-31G(d,p) methods. The relative stability of the various conformers of the uncomplexed 6 is in following order: cone (most stable) > 1-partial-cone ~ 2i-partial-cone > 2-partial-cone ~ 1,3-alternate > 3i-partial-cone. However, the relative stability of the conformational complexes of 6 with is in the following order: 2-partial cone ~ 1,3-alternate > cone > 3-partial cone > 1-partial cone (least stable). The highest binding strengths of 2-partial-cone and 1,3-alternate complexes originate from two strong cation- interactions and two strong cation-oxygen interactions in the complex of 6+. Due to the cation- interactions, the calculated C-C bond distances in the arenes of the -complexes are about 0.0048 longer than the values of their isolated hosts.

It is explicitly shown that a supersymmetry structure exists in the spectrum of a rigid symmetric top rotor in the molecule-fixed frame. Using projection operators constructed from the time-reversal symmetry of the rotor, the full rotor Hamiltonian is separated into two parts, i.e., the bosonic and fermionic components. The construction, without ambiguity, suggests that the rotor has a supersymmetry in it. This supersymmetry is mathematically equivalent to that of the free rotor on a plane recently noted by Rau. ꤠ 돀遠�⨀ 堘�⨀ 袢�⨀ 脠 돐 ꢢ�⨀ ࢷ�⨀ 낢�⨀ 夠 댐 쀅�⨀ 퀅?⨀ �⨀ ㄠ 덐 £�⨀ †

Poly(dimethyl siloxane) (PDMS) has been employed as a microchip material for DNA separation in microfluidic condition. Different sieving molecules such as cellulose derivatives having glucose building block (methyl cellulose (MC), hydroxyethyl cellulose (HEC), and hydroxypropyl methyl cellulose (HPMC)) and polyethylene oxide (PEO) having linear (ring-opened ethylene oxide) unit were used and their performance was compared in terms of separation efficiency and resolution. In general, PEO showed better separation performance than cellulose derivatives probably due to the nature of linear shape polymer conformation. It was possible to perform at least 15 consecutive running with 1.2% PEO at the electric field strength around 200 V/cm. Fast analysis of the standard X 174 RF DNA/Hae III (less than 130s) was obtained with the number of the theoretical plate around 250,000/m. Our PMDS microchip was applied to the measurement of CAG repeat number, which is related to male infertile disease.

Three different style capillary columns, a packed capillary with temporary quartz wool frit, a packed capillary with immobilized frit, and an immobilized packed-capillary, were easily prepared with a commercially available (S)-N-(3,5-dinitro-benzoyl)leucine-N-phenyl-N-alkylamide derived chiral stationary phase. Liquid chromatographic chiral separations of some racemic amino acid derivatives on these columns were performed and the results were compared to each other. The packed capillary with immobilized frit showed some merits in chiral chromatography.

Chemical modification of the S. cerevisiae farnesyl protein transferase (FPT) with CMC, phenylglyoxal and DEPC resulted in enzyme inactivation, depending upon the reagent concentration. The peptide substrate GST-PEP-I, a GST-fused undecapeptide mimicking the C-terminus of , protected the enzyme against inactivation by CMC which is specific to either aspartate or glutamate, while the other substrate farnesyl pyrophosphate (FPP) showed protection against phenylglyoxal which is the specific modifier of arginine residues, dependent on the substrate concentrations. Neither of the two substrates protected the enzyme against histidine inactivation by DEPC. It is suggested that there is at least one aspartate or glutamate residue at the peptide substrate binding site, and that at least one arginine residue is located at the binding site of FPP. There also seems to be at least one histidine residue which is critical for enzymic activity and is exposed toward the bulk solution, excluded from the substrate binding sites.

In our previous studies, we have observed that curcumin and momordin I isolated from Ampelopsis radix inhibit the formation of Fos-Jun-activation protein-1 (AP-1) DNA complex. We have screened more effective compounds which have a 5-membered ring framework like momordin I and have modified disaccharide or carboxylic acid portions in momordin I. We synthesized momordin I derivatives according to the published method with slight modification. Synthetic momordin I derivatives showed remarkable inhibitory activities on Fos-Jun-AP-1 DNA complex formation results in in vitro assays. The values of momordin I derivatives were about 4.0 M in an electrophoretic mobility shift assay (EMSA). This value is about 125 times higher than that of curcumin and about 12 times higher than that for curcumin derivative C1, and moreover about 30 times higher than that for momordin I. We found momordin I derivatives (a) and (b) are the strongest inhibitory compound for Fos-Jun-AP-1 DNA complex formation.

Proton transfer reactions and ion-molecule reactions of bifunctional ethanes of , , and were studied using Fourier transform mass spectrometry (FTMS). The rate constants for proton transfer reactions between the fragment ions and neutral molecules were obtained from the temporal variation of the ion abundances. The rate constants were consistent with the heats of reaction. The fastest proton transfer reactions were the reactions of , , and for , , and , respectively. The ion was formed by the ion-molecule reaction between or and the neutral molecule. The major product ions generated from the ion-molecule reactions between the protonated molecule and neutral molecule were , , and .

We investigated the Surface-enhanced Raman Spectroscopy (SERS) spectrum of ethephone (2-chloroethylphosphonic acid). We observed significant signals in the ordinary Raman spectrum for solid-state ethephone as well as when it was adsorbed on a colloidal silver surface, strong vibrational signals were obtained at a very low concentration. The SERS spectra were obtained by silver colloids that were prepared by the -irradiation method. The influence of pH and the influence of anion on the adsorption orientation were investigated. Two different adsorption mechanisms were deduced, depending on the experimental conditions. The chlorine atom or the chlorine and two oxygen atoms were adsorbed on the colloidal silver surface. Among halide ions, and were more strongly adsorbed on the colloidal silver surfaces. As a result, the adsorption of ethephone was less effective due to their steric hinderance.

Acetohydroxyacid synthase (AHAS, EC 2.2.1.6 also referred to as acetolactate synthase) catalyzes the first common step in the metabolic pathway leading to biosynthesis of the branched-chain amino acids in plants and microorganisms. Due to its presence in plants, AHAS is a target for the herbicides (sulfonylurea and imidazolinone), which act as potent inhibitors of the enzyme. Recently, we have shown [J. Kim, D.G. Baek, Y.T. Kim, J.D. Choi, M.Y. Yoon, Biochem. J. (2004) 384, 59-68] that the residues in the “mobile loop” 567-582 on the C-termini are involved in the binding/stabilization of the active dimer and ThDP (thiamin diphosphate) binding. In this study, we have demonstrated the role of the W573 in the mobile loop of the C-termini of tobacco AHAS. The substitution of this W573 residue caused significant perturbations in the activation process and in the binding site of ThDP. Position W573 plays a structurally important role in the binding of FAD, maintaining the enzyme active site in the required geometry for catalysis to occur. In here we propose that the tryptophan at position 573 is important for the catalytic process.

Studies on Ag nanoparticles grown on Highly Ordered Pyrolytic Graphite (HOPG) using HREELS provide different results for smaller and larger particle sizes corresponding to Ag coverages below and above 4 monolayers, respectively. For the larger particles, a positive frequency shift with decreasing particle size and a broadening of the plasmon resonance were observed with decreasing particle size, in line with previous studies on Ag on alumina. For the smaller particles, in contrast, a shift to lower energy with decreasing particle size, and a narrowing of the plasmon resonance with decreasing particle size can be found. The asymmetry of the Ag-features present for Ag coverages above 4 monolayers disappears for Ag coverages below 4 monolayers. The result for the smaller particles can be rationalized in terms of change of the particle growth mode with increasing particle size, which corroborates our STM data, as well as electronic effects due to the metal/support charge transfer.

The application of a synergistic solvent extraction by the formation of ternary complex with pyrocatechol violet (PV) and benzalkonium chloride (BC) was studied for determination of trace Zn(II) in water samples. The pH of sample solution and the amount of PV and BC added were optimized for the formation of the stable complex, a proper solvent was selected for the effective extraction, and the concentration of nitric acid was fixed for the back extraction of the complex from the solvent. After the ionic strength of 100 mL sample solution was adjusted to 0.1 M by adding NaCl and the pH was fixed at 9 with a carbonate buffer, 1.0 mL of 2% PV solution was added to form Zn(II)-PV complex then the Zn(II)-PV/BC ternary complex was made by adding 1.0 mL of 10% BC solution. The ternary complex was extracted into 10 mL of MIBK. And the ternary complex was back-extracted with 10 mL of 1.0 mol/L nitric acid to determine Zn(II) by a flame atomic absorption spectrophotometer (flame-AAS). The interference of concomitant ions on the extraction of Zn(II) was investigated. This procedure was applied to the analysis of three real samples such as Dalbang-dam water, laboratory tap water and Jungnajin seawater. The recoveries of Zn(II) in spiked samples were 86.58-104.1%.

To study the effect of sequence on DNA structure, the two decamer crystal structures one alternating,d(GTACGCGTAC), and the other non-alternating, d(GGCCGCGGCC), were solved. Crystals of both decamers belong to the hexagonal space group , with one strand in the asymmetric unit. The unit cell constants of the alternating decamer are a = b = 39.26 , c = 77.70 . The structure was refined with 1,828 reflections from 8.0 to 2.0 Aresolution to an R value of 21.3% with all DNA atoms and 63 water molecules. The isomorphous non-alternating decamer had unit cell dimensions of a = b = 39.05 , c = 82.15 . The structure was refined with 2,423 reflections from 8.0 to 2.0 resolution to a final R value of 22.2% for all DNA atoms and 65 water molecules. Although the average helical parameters of the decamers are typical of A-DNAs, there are some minor differences between them. The helical twist, rise, x-displacement, inclination and roll alternate in the alternating decamer, but do not in the non-alternating decamer. The backbone conformations in both structures show some differences; the residue G(7) of the alternating decamer is trans for and while the trans conformations are observed at the residue G(8) of the non-alternating decamer.